JPH06287155A - Production of alkadienol - Google Patents

Abstract

PURPOSE:To provide an industrially advantageous method capable of producing an alkadienol in high selectivity and yield with high production thereof per unit time and the amount of catalyst. CONSTITUTION:Using as catalyst a palladium compound and a phosphine compound, a reaction is conducted between water and a conjugated alkadiene in the presence of carbon dioxide to obtain the objective alkadienol. In this case, the molar ratio of the phosphorus atoms present in the form of a vinylphosphonium salt in the reaction liquor to the total phosphorus atoms in the reaction liquor is 0.001 to 0.5.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing alkadienols. More specifically, the present invention uses a palladium compound and a phosphine compound as a catalyst to react a conjugated alkadiene with water in the presence of carbon dioxide to give an alkadienol which is a dimerized hydrate of the conjugated alkadiene. The present invention relates to an improvement in manufacturing method.

[0002]

BACKGROUND OF THE INVENTION Alkadienols, especially octa-2,
Octadienols such as 7-dien-1-ol are important chemical and industrial compounds as intermediates for producing n-octanol or its ester. As a method for producing such alkadienols,
Conventionally, a method of producing a dimer hydrate alkadienols by reacting a conjugated alkadiene with water in the presence of carbon dioxide using a palladium compound and a phosphine compound as a catalyst is disclosed in, for example, Chemical Communications (Chemical Communications). Communication
s), 330, (1971), and Japanese Examined Patent Publication No. 50-105.
It is known by No. 65 and the like. In this case, triphenylphosphine is known to be advantageous as the phosphine compound used as the ligand of the palladium compound, but the yield and selectivity of the alkadienols and the activity of the catalyst are still insufficient. Not a thing. Further, it is known that the use of triphenylphosphine in an excess of about 6 times with respect to palladium lowers the yield of alkadienols (Chemical Communications), and the problem of being restricted by operating conditions. There was also.

On the other hand, the form of the catalyst in the reaction solution in the above reaction has not been sufficiently studied, and it was considered that the phosphine compound usually exists as a phosphonium salt in the reaction solution.

[0004]

The metal component used in the catalyst plays an important role in the complex catalytic reaction. The kind of the ligand used together with it and the selection of the reaction conditions determine the activity of the catalytic reaction and the Significantly affects selectivity. The present inventors have used a palladium compound and a phosphine compound as a catalyst to dilute a desired alkadienol with a highly active catalyst system in a dimerization hydration reaction in which a conjugated alkadiene and water are reacted in the presence of carbon dioxide. The inventors have made earnest studies to provide an industrially advantageous method for producing octadienols which can be obtained in high yield and high selectivity.

[0005]

The method for producing alkadienols according to the present invention comprises using a palladium compound and a phosphine compound as catalysts and reacting a conjugated alkadiene with water in the presence of carbon dioxide to give an alkadienol. In the method for producing compounds, the proportion of phosphorus atoms present as a vinylphosphonium salt in the reaction solution with respect to all phosphorus atoms in the reaction solution is 0.1 mol% or more and 50 mol% or less. That is, the present inventors, in a method of reacting a conjugated alkadiene and water in the presence of carbon dioxide to produce a dimer hydrate alkadienols,
The abundance ratio of phosphorus atoms existing as a vinylphosphonium salt in the reaction solution to the total phosphorus atoms in the reaction solution is 0.1.
By carrying out the reaction under the conditions of not less than mol% and not more than 50 mol%, the catalyst component is effectively and efficiently utilized, and the amount of alkadienols obtained per palladium is dramatically increased. High yield of alkadienols,
The inventors have found that a high selectivity can be obtained and have reached the present invention.

The present invention will be described in detail below. The greatest feature of the present invention is that the proportion of phosphorus atoms present as a vinylphosphonium salt in the reaction solution to the total phosphorus atoms in the reaction solution is 0.1 mol% or more and 50 mol% or less. Here, the abundance ratio in the reaction solution means that the abundance ratio is 0.1 mol% or more and 50 mol% or less when the reaction liquid is extracted from the reaction system and analyzed during or after the reaction. .

On the other hand, the vinylphosphonium salt here means
Vinylene group in which 4 carbon atoms are substituted in the phosphorus atom and which is directly bonded to the phosphorus atom (however, it may have a substituent)
Is not particularly limited as long as it is a quaternary phosphonium salt having
Usually, a vinylphosphonium salt produced by the reaction of an olefinic compound and a phosphine compound present in the reaction solution can be mentioned. Specific examples thereof include vinylphosphonium salts represented by the following formula (III), which are produced by the reaction of allyl alcohols represented by the following formula (I) and a phosphine compound represented by the following formula (II). .

[0008]

[Chemical 1]

(In the above formulas (I) to (III), R ¹ ,
R ² and R ³ each represent a hydrogen atom or a hydrocarbon group having 1 to 13 carbon atoms which may have a substituent,
R ⁴ , R ⁵ and R ⁶ each represent a hydrocarbon group having 1 to 14 carbon atoms which may have a substituent, and X represents a hydroxyl group, a hydroxycarbonyloxy group or a lower alkylcarbonyloxy group. ) The proportion of the vinylphosphonium salt present is such that the phosphorus-N in the reaction solution immediately after the reaction under normal temperature and pressure.
It can be easily determined by taking MR. In the reaction solution,
The proportion of phosphorus atoms present as a vinylphosphonium salt relative to all phosphorus atoms in the reaction solution is 0.1 mol% or more and 50 mol% or less, preferably 1 mol% or more and 40 mol% or less, more preferably 2 mol% or more. It is preferably 20 mol% or less from the viewpoint of effectively and efficiently utilizing the catalyst component, and in this case, the reaction advantageously proceeds even at a low palladium concentration.

In the present invention, the reaction conditions are not particularly limited as long as the ratio of phosphorus atoms present as a vinylphosphonium salt in the reaction solution to the total phosphorus atoms in the reaction solution is in the above range, but the reaction conditions are as follows. By selecting the reaction conditions such as the kind of the phosphine compound and the ratio of the phosphine compound and palladium as described above, the abundance ratio of the vinylphosphonium salt in the reaction solution can be maintained within a specific range, which is industrially advantageous. It is possible to manufacture

Conjugated alkadienes for producing alkadienols by reacting with water by the method of the present invention include 1,3-butadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1, 3-butadiene, isoprene, 1,3-pentadiene, chloroprene, 1,3-
Octadiene and the like. When the starting material is 1,3-butadiene, those which are usually easily available include purified 1,3-butadiene and a so-called BBP, that is, a C ₄ fraction mixture in a naphtha decomposition product.

When BBP is used as a raw material mainly in consideration of economy, it is desirable to separate and remove acetylenes and allenes contained in the raw material BBP in advance. The method for reducing acetylenes and allenes is not particularly limited, and various known methods can be appropriately adopted. After removing or reducing acetylenes and allenes, the total concentration of acetylenes and allenes in the 1,3-butadiene raw material to be subjected to a dimerization hydration reaction for producing octadienol is possible. It is desirable to be as low as possible, but usually, it is preferably about 1.0% by weight or less relative to 1,3-butadiene.

On the other hand, as the other raw material water, water having a purity that does not affect the dimerization hydration reaction is appropriately used. Although the amount of water used is not particularly limited,
It is usually selected from the range of 0.5 to 10 mol, preferably 1 to 5 mol, relative to 1 mol of 3-butadiene. In the present invention, a palladium compound is used as the main catalyst. The form of the palladium compound used and its valence state are not necessarily limited. Bis (phosphine) palladium having a phosphine compound used as a cocatalyst as a ligand, tris (phosphine) palladium, tetrakis (phosphine) palladium, tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, (1,5
-Cyclooctadiene) (maleic anhydride) 0-valent palladium complex such as palladium; palladium inorganic acid salt such as palladium nitrate; palladium organic acid salt such as palladium acetate;
Examples thereof include bivalent palladium complexes such as bis (acetylacetone) palladium and bis (tri-butylphosphine) palladium acetate.

The amount of the palladium compound used can be varied over a wide range, but is usually selected within the range of 0.000002-1 gram atom, preferably 0.00002-0.1 gram atom as palladium per mol of the conjugated alkadiene. . According to the method of the present invention, the catalyst component in the reaction solution is used more effectively, so that 0.00002-0.
The reaction works well even within a very low palladium concentration range of 0002 gram atom.

On the other hand, the kind of phosphine compound used as a cocatalyst includes trialkylphosphine, dialkylmonoarylphosphine, monoalkyldiarylphosphine, triarylphosphine and the like, which are conventionally known, and particularly monoalkyldiarylphosphine. , And triarylphosphine are preferred. Examples of such compounds include trialkylphosphines, dialkylmonoarylphosphines, monoalkyldiarylphosphines, and triarylphosphines, with monoalkyldiarylphosphines and triarylphosphines being particularly preferred. For example,
Triphenylphosphine, tri (tolyl) phosphine,
Di (tolyl) (phenyl) phosphine, (tolyl) di (phenyl) phosphine, tri (ethylphenyl) phosphine, di (ethylphenyl) (phenyl) phosphine, (ethylphenyl) di (phenyl) phosphine, tri (xylyl) phosphine , Tri (mesityl) phosphine, tri (tetramethylphenyl) phosphine, tri (methylmethoxyphenyl) phosphine and other hydrophobic phosphine compounds and tri (4- (2-sodium sulfonate ethyl) phenyl) phosphine, phenyldi (4-
(2-sodium sulfonate ethyl) phenyl) phosphine, diphenyl (4- (2-sodium sulfonate ethyl) phenyl) phosphine, tri (4- (2-sodium sulfonate ethyl) tolyl) phosphine, tolyldi (4- (2-sodium sulfonate) Examples thereof include hydrophilic phosphines such as ethyl) tolyl) phosphine, ditolyl (4- (2-sodium sulfonate ethyl) tolyl) phosphine, and tri (2-methyl-4-N, N-dimethylaminophenyl) phosphine.

In the present invention, it is necessary to carry out the reaction with the proportion of phosphorus atoms present as the vinylphosphonium salt present in the reaction solution in a specific range, and therefore the amount of the phosphine compound used is usually 1 gram atom of palladium. However, it is preferably 3 mol to 150 mol, more preferably 10 mol to 100 mol. The amount of the phosphine compound used is preferably within the above range so that it can be dissolved in the reaction solution under the reaction conditions. In addition, the reaction may be performed while adding a phosphine compound to the extent that it is dissolved in the reaction solution during the reaction.

The reaction of the conjugated alkadiene of the present invention with water is carried out in the presence of carbon dioxide using the above-mentioned palladium compound and phosphine compound as catalysts. The carbon dioxide used in the present invention may be any carbon dioxide existing in the reaction system as carbon dioxide, and its supply form is not particularly limited. Examples thereof include molecular carbon dioxide, carbonic acid, carbonates, bicarbonates, and carbon dioxide or an adduct of carbonic acid with an amine. The upper limit of the amount of carbon dioxide used is determined for economic reasons, and even if it is used in excess, it does not particularly hinder the reaction. Usually, carbon dioxide is used in an amount of 1 mol or more, preferably 10 mol or more, based on 1 gram atom of palladium.

In carrying out the reaction between the conjugated alkadiene and water, it is preferable to use a solvent in order to carry out the reaction more smoothly. As a solvent that can be used, ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, acetone,
Ketones such as methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone and ethyl-n-butyl ketone, nitriles such as acetonitrile, propionitrile and benzonitrile, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, pentane, hexane, Alkanes such as heptane, alkenes of hexene and octene, sulfoxides such as dimethyl sulfoxide, sulfones such as sulfolane, nitro compounds such as nitrobenzene and nitromethane, pyridine derivatives such as pyridine and α-picoline, amines such as triethylamine Amides such as acetamide, propionamide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, methanol, ethanol,
Examples thereof include alcohols such as n-propanol, isopropanol, n-butanol, isobutanol, t-butanol and n-octanol, and carboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid. When such solvents are used, they may be used alone or as a mixed solvent. Among these, particularly when lower alcohols are used, by-products such as alkoxyoctadiene are not produced, and when lower carboxylic acids are used, by-products such as acyloctadiene are produced. No, both require caution because it complicates the reaction system.

Although the amount of the solvent used is not necessarily limited, it is usually selected arbitrarily from the range of 0.1 to 50 parts by weight, preferably 1 to 10 parts by weight per 1 part by weight of the conjugated alkadiene. It The method of the present invention can be carried out using known techniques such as continuous, semi-continuous, and batch operations.

The reaction temperature for reacting the conjugated alkadiene with water can be selected from the range of room temperature to about 180 ° C., but it is more general to select the temperature range of about 50 to 130 ° C. Preferably, 75-100 ° C
Is more desirable. Reaction pressure is from normal pressure to 200
It is selected from the range of about kg / cm ² . At this time, in addition to carbon dioxide, it is also possible to coexist with an inert gas such as nitrogen, helium, and argon in the reaction.

In the present invention, the conjugated alkadiene is reacted with water under the reaction raw materials and the reaction conditions described above to produce an alkadienols. In the reaction product liquid obtained by this reaction, the catalyst, the main product alkadienol, by-products alkatrienes, dialkadienyl ethers, organic carboxylic acids and esters,
In addition, the solvent, unreacted conjugated alkadiene, water and the like are contained. When the starting material conjugated alkadiene is 1,3-butadiene, octa-2,7-dien-1-ol is the main product, and octa-1,7-dien-3-ol and octatrienes are the by-products. , Dioctadienyl ethers and organic carboxylic acids. The amount of by-products produced depends on the reaction conditions, and is usually within a few mol% on the basis of the conjugated alkadiene. After the reaction, the alkadienols can be recovered by a known means such as distillation, if desired.

[0022]

The present invention will be further described with reference to the following examples.
The present invention is not limited to the following examples unless it exceeds the gist. In the following examples, ΣHOD yield, 1HOD / ΣHOD, ΣHOD selectivity, P ′ / Pd and TOF have the following meanings.

ΣHOD Yield: Yield (%) of produced octadienols to charged butadiene 1-HOD / ΣHOD: Ratio of octa-2,7-dien-ol (1-HOD) in octadienols ( %) ΣHOD selectivity: Selectivity of reacted octadienols to butadiene reacted (%) vinyl P ⁺ : Ratio of phosphorus atoms existing as vinylphosphonium salt to all phosphorus atoms detected by P-NMR TOF : Number of moles of butadiene converted to octadienol per 1 gram atom of palladium used per hour

Example 1 In a stainless steel autoclave having an internal volume of 200 ml, 0.0625 mmol of palladium acetate (initial Pd concentration in the reaction solution: 125 ppm) was added in a nitrogen gas atmosphere.
3.0 mmol tri (o-methylphenyl) phosphine (initial P concentration in reaction solution (as phosphine compound) 8100 ppm), 47 ml acetone, 6.7.
Then, 1 ml of 1,3-butadiene and 8 g of carbon dioxide were introduced. 800 reaction mixture
The internal temperature is 7 for 20 minutes while stirring at the speed of rpm.
Heated to 5 ° C. After continuing the reaction at 75 ° C. for 4 hours, the reaction solution was analyzed by gas chromatography and P-NMR. The results are shown in Table-1 and Table-2.

Example 2 The same reaction as in Example 1 was carried out except that the amount of tri (o-methylphenyl) phosphine used was 2.0 mmol. The results are shown in Table-1 and Table-2.

Example 3 In Example 1, the amount of palladium acetate used was 0.12.
The reaction was carried out in the same manner except that 6.0 mmol of tri (2,4-dimethylphenyl) phosphine was used instead of tri (o-methylphenyl) phosphine in 5 mmol. The results are shown in Table-1 and Table-2.

Example 4 In Example 1, the amount of palladium acetate used was 0.12.
The same reaction was carried out except that 4.0 mmol of tri (2,4-dimethylphenyl) phosphine was used instead of tri (o-methylphenyl) phosphine in 5 mmol. The results are shown in Table-1 and Table-2.

Example 5 In Example 1, 0.0625 mmol of bis (acetylacetone) palladium was used instead of palladium acetate,
The reaction was performed in the same manner except that 2.0 mmol of tri (o-ethylphenyl) phosphine was used instead of tri (o-methylphenyl) phosphine and the reaction temperature was 90 ° C. The results are shown in Table-1 and Table-2.

Comparative Example 1 In Example 1, the amount of palladium acetate used was 0.12.
The same reaction was carried out except that 4.0 mmol of tri (2-methyl-4-methoxyphenyl) phosphine was used instead of tri (o-methylphenyl) phosphine in 5 mmol. The results are shown in Table-1 and Table-2.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

According to the method of the present invention, a conjugated alkadiene is reacted with water in the presence of carbon dioxide using a palladium compound and a phosphine compound as a catalyst to produce an alkadienols with high yield and high selectivity. The present invention provides a method for industrially advantageous production of alkadienols, which is capable of producing a large amount of a catalyst and has a large amount of alkadienol produced per unit time.

Claims (1)

[Claims] 1. A method for producing an alkadienols by reacting a conjugated alkadiene with water in the presence of carbon dioxide using a palladium compound and a phosphine compound as a catalyst, which is present as a vinylphosphonium salt in a reaction solution. The method for producing an alkadienols, wherein the ratio of the phosphorus atoms present to all the phosphorus atoms in the reaction solution is 0.1 mol% or more and 50 mol% or less.